Mild Hydrothermal Crystal Growth, Structure, and Magnetic Properties of Ternary U(IV) Containing Fluorides: LiUF5, KU2F9, K7U6F31, RbUF5, RbU2F9, and RbU3F13

Single crystals of several ternary alkali uranium fluorides, LiUF5, KU2F9, K7U6F31, RbUF5, RbU2F9, and RbU3F13, have been obtained in a mild hydrothermal process using UO2(CH3CO2)2(H2O)2 as the uranium source. Their crystal structures were determined by single crystal X-ray diffraction. The uranium in the starting reagent was successfully reduced from U6+ to U4+ in a dilute hydrofluoric acid environment, aided by the presence of a copper salt. All materials exhibit highly complex crystal structures that range from two-dimensional to three-dimensional. The U4+ cations are found in high (UF8 and UF9) coordination environments. The magnetic susceptibility measurements yielded effective magnetic moments of 3.01–3.83 μB for the U4+ cations. The temperature dependent magnetic susceptibility measurements confirmed that the U4+ cation exhibits a nonmagnetic singlet ground state at low temperatures. No long-range magnetic order was observed for any of the above compositions down to 2 K. Optical and thermal behaviors of the fluorides were also investigated.